Vulcanization bonding of ethylene alpha-olefin copolymer with a chlorosulfonated copolymer inner layer



' limited reciprocal diffusion of their molecules.

United States Patent 3,260,641 VULCANIZATION BONDING OF ETHYLENE ALPHA-OLEFIN COPOLYMER WETH A CHLOROSULFONATED COPOLYMER INNER LAYER Luigi Falcone, Milan, Italy, assignor to Montecatini, Societa Generale per llndustria Mineraria e Chimica, Milan, Italy, a corporation of Italy No Drawing. Filed May 26, 1961, Ser. No. 112,784 8 Claims. (Cl. 161-242) The present invention relates to the preparation of co-v-ulcanizable mixes and vulcanized articles containing successive layers of natural or synthetic rubber, modified olefin copolymers and unmodified copolymers. Natural rubber, as is well known in the art is uncured and unvulcanized. More particularly, the present invention relates to mixes containing layers of natural or synthetic rubber, a copolymer of ethylene with propylene or butene-l containing chlorosulphonic groups, which copolymer may be mixed with rubber or other resins, and an unmodified copolymer of ethylene with propylene or butene-l.

In the field of synthetic rubbers, compatibility with natural rubber is considered a valuable property.

This compatibility is often considered only in terms of the possibility of co-vulcanization. Olefin copolymers of ethylene with propylene or butene-l, due to their parafiinic nature, can be co-vulcanized with natural rubber with the aid of organic peroxides as vulcanizing agents. The olefin copolymer and natural rubber can be mixed in a roll mixer and the end product appears to be homogeneous. However, if these two compounds are merely contacted and then subjected to vulcanization by heating in a press, it is observed that the two layers can easily be separated. There is therefore a difference between a compatibility with the vulcanizing agents and a physical compatibility depending on how easily the different molecules of the natural synthetic rubber and the olefin copolymer can diffuse through each other. Thus, the compatibility of a vulcanizing agent with both both types of polymer material does not imply the physical compatibility of one polymer with the other.

If reference is made to the free mixing energy (as defined e.g., in Principles of Polymer Chemistry, P. Flory, 1953, page 507), it can be seen that in the field of macromolecular substances the reciprocal diffusion of different molecules is not favored thermodynamically because of the low entropy contribution which results from the relatively small number of molecules involved.

The Copolymers of ethylene with propylene or butene-l, it is found, are completely incompartible with natural or synthetic rubber owing to the difference in the chemical structures of the two substances and to the Olefin copolymers are substantially completely saturated while natural or synthetic rubber is highly unsaturated. For several industrial applications it would be extremely useful to have co-vulcanizable mixes which would thus lead to the production of vulcanized articles containing natural or synthetic rubber and olefin copolymer layers tightly sealed to each other giving products which combine the good properties of natural rubber with the valuable characteristics of a saturated elastomer.

The present invention provides co-vulcanizable mixes and, thus, vulcanized articles of natural or syntheic rubber and an olefin copolymer, in which both substances are firmly joined to each other. Under synthetic rubber, rubbers structurally similar to natural rubber such as polybutadiene 1-4 cis and polyisoprene 1-4 cis are meant. It has been found that when chlorosulphonic groups are introduced into the olefin copolymer, the re- 3,260,641 Patented July 12, 1966 suiting chlorosulphonated copolymer functions to make the unmodified copolymer physically compatible with natural rubber. If two layers, comprising natural or synthetic rubber and a chlorosulphonated copolymer, respectively, are heated in a press, the fusion of the two layers is surprisingly achieved. This fusion leads to a considerable molecular diffusion between the two substances and the formation, and in the presence of vulcanizing agents leads to the formation of mixed bridges between the copolymer and the rubber.

The present invention also provides a method of vulcanizing an olefin copolymer onto a support material using a chlorosulphonated olefin copolymer as an adhesive.

The chlorosulphonated copolymer appears to be physically compatible with the untreated olefin copolyrner as such. This makes it possible to obtain the desired adhesion of the copolymer to natural or synthetic rubber by interposin-g a layer of chlorosulphonated copolymer. It has been found that the layer of modified copolymer can be replaced by an adhesive prepared by dissolving the chlorosulphonated copolymer in a hydrocarbon solvent of the aliphatic series, such as heptane, a solvent of the aromatic series, such as toluene, or by dissolving in a chlorinated hydrocarbon such as carbon tetrachloride.

An advantage of the present invention is that the undesired interference of conventional vulcanization agents for diolefin rubbers such as sulphur and the like and conventional rubber accelerators such as diphenyl guanidine and the like, with the action of the peroxide vulcanizing agents for the copolymer, is avoided by this intermediate chlorosulphonated copolymer layer which prevents direct contact between the treating agents for the two different materials. This permits the co-existence and the separate action of the different agents in their respective external layers and a surprisingly synergic vulcanisation in the intermediate layer of chlorosulphonated copolymers, the amounts of the vulcanizing agents being the same. The use of the underlayer or adhesive of the Y Modern Plastic Encyclopedia, 1961, Adhesive Chart.

These resin materials impart to the chlorosulphonated copolyrner the adhesivity required for the cold shaping of articles.

Other advantages and objects of the present invention will be obvious from the following description and working examples.

Copolymers of ethylene with propylene or butene-l and the methods for vulcanizing them are described in British Patent Specifications 856,736 and 856,737, respectively. These copolymers contain from 10% to ethylene by mols and have a molecular weight (viscosimetrically determined: see the article of Mora-glio in La Chimica e lIndustria 41, 984, 1959) of from 50,000 to 600,000 and above. They can be vulcanized with various vulcanizing agents, but, according to the present invention, vulcanization is preferably carried out with peroxides and sulphur, in ratios of amounts of sulphur to peroxide between 01:1 and 3:1 preferably 0.321 and 1.5 :1, most preferably 1 gram atomic weight sulphur per 1 mol peroxide. The chlorosulphonated copolymer contains from 0.5% to 35%, preferably from 5% to aae eal 25% chlorine and from 0.01% to preferably from 0.1 to 3% sulphur. Any monoor di-peroxide suitable in the vulcanization of saturated, amorphous polymers such as cumyl-, ditert. buty1-, diter. butyltetrachloride, 2-5 dirnethyl (2,5- diperoxiditerbutyl)-hexane, -peroxide may be used. The vulcanization is carried out at from 120 to 220 C. preferably from 140 to 180 C.

The present invention is illustrated but not limited by the following examples:

Example 1 In Table I is reported the composition of the certain mixes according to the present invention. In Table II is shown compositions of the chlorosulphonated copolymer-based adhesives. In Table II is shown the results of the peeling tests carried out according to ASTM D 413-39. The specimens containing the adhesive layer were vulcanized in a press for 40 minutes at 165 C.

The chlorosulphonated copolymer used had a chlorine content of about and a sulphur content of 1% to 1.5

TABLE I Composition of the Mix Ingredients a b t c d Copolymcr ethylene-propylene or ethylenebutene containing 50% moles ethy1ene- 100 100 Natural rubber 100 100 Carbon black HAF (high abrasion iurnac ga gbon black EPC (casy processing channe n gurosil (silica) TABLE II Composition of the dhesive Ingredients CS CS CS CS Chlorosulphonated copolymer C -C5 Natural rubber 102 flaiebon black SAF (super abrasion furnace) Staybelite (rosin resin) Phthalic acid Thiuram M (tetramethyl thiuram disulphide) Tetram A Durosil (silica) 4. Example 2 A chlorine and sulphur dioxide current is passed through a solution of ethylene-propylene copolymer in carbon tetrachloride under actinic radiation. The copolymer is about :50 mols percent ethylene-propylene and has a molecular Weight of about 150,000. When the reaction is completed a product containing about 15% chlorine and about 1.5% sulphur is isolated. Using the chlorosulphonated copolymers, mixes are prepared in a roll mixer as reported in Table IV. The mixes thus obtained are dissolved in heptane and the adhesives obtained are indicated by CS.

TABLE IV Composition of the Adhesives Ingredients CS CS CS CS Chlorosulphonated copolymer (ethylene-propylene, ethylene-butene) 100 100 Natural rubber. 20 Durosil (silica) 50 50 10g I a 20 20 Carbon black sion furna 50 MgO 2 2 2 D iphenylguanidine 1 1 1 Tertiary butyl cumyl per 3 3 3 Sulphur 2. 8 2. 8 2. 8 Staybcllite (rosin resin) Phthalie acid Thiurarn M (tetrarnethyl thiuram disulphide) Tetroue A (dipenta methylene-thiuram tetrasulphide) TABLE V Composition of the Mixes Ingredients a b o d e f bber Carbon black HAF (high abrasion furnace Carbon black IPC (intermediat processing channel n Durosil (silica) MgO Sautocure (cyclohexyl sulpham dc) Diphenylguanidine Sulphur Tertiary butyl cumyl pero. dc

The adhesive is spread in the form of a very thin layer onto the contact surfaces of the copolymer and natural rubber and vulcanization is carried out in a press at Cz-C =ethylene-pr0py1ene copolymer. 55 C. for 40 minutes.

TABLE III Peeling Values Rubber Ply Michelin Copolymer Copolymer Copolymer Adhesives (a) (b) b GN l (c) GN (c) GN (d) Copolymer Copolyrner kgJcm. lb./in. kg./cm. lb./in. kg./cm. lb./in. kgJcm. lb./in. kgJcm. lb./in.

13 13 13 CS4 8 Natural rubber solution plus peroxide and sulphur 5 28. 0 Without adhesive. 3 16. 8

Legend 1 GN Natural rubber. 2 Rubber detaches from the ply.

3 Specimen breaks outside the adhesion surface. 4 Does not adhere.

5 From the sheets thus obtained, some specimens are prepared. These specimens are then subjected to peeling tests according to ASTM D 413-39. In Table VI the results obtained, express as kg./crn. and pounds/inch, are

technique used in apparatus of the bag-o-matic type at about 12 atmospheres with water vapor. The vulcanizing is then carried out for about I hour with steam under 7 atmospheres inside the bladder and under 8 atmospheres Tertiary butyl cumyl peroxide 2 The plies were cut at an angle of 60 and were placed with their edges on a drum.

reported. 5 outside the mold. The tire thus prepared is tested for TABLE VI Peeling values-Joined mixes Adhesives a-c b-c b-d kg./cni. pounds/ kg./em. pounds/ kgJcm. pounds] inch inch inch CS1 13 72. s 17 95. 2 16 89.6 CS 13 72.8 CS3 13 72.8 cs 8 44. 8 12 67. 2 i 56. 0

Legend- 1 Specimen breaks outside the adhesion surface.

Example 3 2,000 km. on a knurled-surface road-wheel having a Adhesive CS of Table IV is employed for joining mixes dlameter of 35 Wlth aX1a1 load of 1 a of copolymer (see Table V) and a comme i l rubber. speed of 80 km./hour. During the test the tire reaches a coated fabric. In the tensile tests the peeling value be- 25 temperature of out 60 on the outer surface. More tween copolymer and natural rubber cannot be determined Sew/1'6 tests are also can'led out mcreaslng aXlal since during the tension the weaker bond, that is, the f Wlth a load of 250 g 1t 18 Observed that t natural rubber-to-fabric bond gives way. The results of P break after a f hours, 111 the area of the h h these tests are reported in Table VII, in which they are Zone, but Separatlon the tread from the P compared with a test carried out with an adhesive based 39 e A the P p 111 the saihe e but d on natural rubber and with a test in which the copolymer entirely of natural rubber behaves in a similar manner in surface is contacted directly with the natural rubber surthe tests 011 the TOad'WheeL face.

E The adhesive based on natural rubber was prepared by 'xample 5 dissolving in heptane a natural rubber mix having the 3:) A worn 5.20-14 car tire was rasped and retreaded with following composition: a tread made of unmodified copolymer (mix of Example N t 1 bb 100 4). An under-layer of natural rubber (mix d, Table V) E X 50 was interposed between the tread and the carcass. The b f 1 ""12 2 use of this under-layer makes the application of the tread g y cumy peroxl e 0 3 to the carcass easier. Adhesive CS (Table IV) was used H P m as a binder between the natural rubber under-layer and Table Pp the copolymer tread, while in order to facilitate the join- Example 4 ing of the under-layer to the carcass, which is made of A scooter-tire (size 4.008) was prepared from plies vulcfimzeti natural rubbep an adhe.slve prepared by d13- coated with conventional natural rubber and treads con- 0 fi E d 9 j v m h g g h d sisting of the following mix containing an unmodified e V Camza ou 2 Ours un er ethy1ene pr O Pyle ne copolymer: 8 atmospheres of steam, with a molding pressure, ob-

tained with water pressure of about 20 atmospheres. The p ym r 100 tire, tested on the knurled road-wheel with a diameter Carbon black HAF 50 of 88 cm., for 2000 km. at a speed of km./hour with Sulphur 0- an axial load of 500 kg., did not show any stripping.

The tire was then destroyed and in the portion corresponding to the adhesion zone, a peeling value of 18 kg./ cm. is found.

TABLE VII.-ADHESION TO COMMERCIAL RUBBER-COATED FABRICS Copolyiner Mix Used Adhesive a b o d kg./crn. p./ineh kg./cm. p.linch kgJcm. p./inch kg./cin. p./inch CS 12 1 67. 2 12 1 67. 2 1 12 67. 2 1 1 12 1 67.2 Natural rubber adhesive 3 16. 8 5 28. 0 2 11. 2 4 22. 4 Without adhesive 3 16. 8 2 11. 2 4 22. 4

Legend- 1 Natural rubber is stripped from the fabric. 2 Does not adhere. Thereafter, adhesive CS (Table IV) was spread on 7 0 Example 6 the larger base of the trapezoidal extruded tread, and a very thin layer (about 0.8 mm.) of natural rubber, contained from mix d of Table V was applied thereon.

The tread is then placed on the rubber-coated plies supported by the drum. The shaping is carried out with the A conveyor belt, having a width of cm. and a thickness of 0.9 cm., is prepared with commercial rubber-coated cloths. Three of these cloths were assembled and then interposed between two copolymer sheets having a thickness of 3 and 2 THIIL, respectively. Adhesive CS Copolymer 100 Carbon black ISAF 60 Sulphur 0.3

Di-tertiary butyl cumyl peroxide 2 Example 7 A chlorine and sulphur dioxide current is passed through an ethylene-butene copolymer solution in 001.; under actinic radiation. The copolymer had the following characteristics Ethylene content, mol percent 50 Molecular weight 130,000

Example 9.Adhesin of ethylene-propylene copolymer to fabrics A cord type rayon fabric treated according to a known method with a resorcinol-formaldehyde resin in a natural rubber latex, was immersed in a heptane solution of sulphorchlorin-ated polymer (mix CS and CS see Table IV). The fabric is suitably wrung and then dried in a current of warm air. Yarns of the cord are then taken and used for carrying out some tests of adhesion to ethylene-propylene copolymers (mix a; see Table V), according -to the method H Test. (Rubber Chemistry and Technology; Volume XX; Number 1, 1947; page 268.)

In Table X are reported the conditions of the test and the values of adhesion between the cord" fabric and the copolymer mix.

The results show the improvements obtained by pretreating the fabric with a solution of sulphochlorinated polymer.

TABLE X Test Conditions- Diameter of the yarn, mm Working length of the yarn, mm- Adhesion surface of the yarn, cm Tractive speed, nan/minute At the end of the reaction (after about 1 hour), the Results copolymer had a chlorine content of 12% and a sulphur 0 Resistance to Peeling Average Notes e 1 content of 1.8%. Using this chlorosulphonated copolykg. cm. Value mer, the mixes reported in Table IV were prepared. The various mixes thus obtained were dissolved in heptane 52. -71. 5-3110 Fabric treated withasolution and the adhesives obtained are indicated by CS in Table no igigjjgj 51.9 gl Polymer IV. 41.0

In Table V, Columns e a Z" the Vanous mlxes 47.3-57.1-451 50 19 Fabric treated withasolution used are reported. The adhesive is employed as de- 5. 3.9- -6 ofsulphochlorinated p y scribed in Example 2. The vulcanization and the peeling (084) tests are carried out as in Example 2. The results, ex- 35 :52. -3213-326 26 Fabric not treateglwithasolupressed as kg./cm. and pounds/inch are reported in Ta- (mated ble VIII.

TABLE VIII Joined Mixes Adhesives e-c f-c f-d kgJem pounds/ kgJem. pounds/ kg./em. pounds] inch inch inch The adhesives of the example may be employed in the Example 10 same applications as described in Examples 3 to 6', with the obtaining of results similar to those obtained with adhesives containing chlorosulphonated ethylene-propylene copolymers.

Example 8.Aa'hesi0n of ethylene-propylene copolymer tometals Tests were carried out according to ASTM D 429-56 T, using carbon steel plates. A layer of resorcinol-formaldehyde resin was spread onto the metal; either no adhesive or the adhesive CS (Table IV) was spread on mix a (Table V). The test and the results are reported in Table IX. It will be seen that the use of the adhesive improves the resistance to peeling considerably. Analogous results were obtained using adhesives CS CS and CS TABLE IX Combination Resistance to Peeling,

kgJemJ Metal- Resorcinol-formaldehyde resin, Mix a -25-23-30-26 etal- Resoreinol-iormaldehyde resin CS, Mix a 46-47-36-52-45 The peeling tests were carried out on different specimens according to the above ASTM D 41339.

In following example a further feature advantage of the use of chlorosulfonated copolymer in the retreading of big tires or in the integral retreading of normal tires is pointed out; in these cases a central strip, two strained pieces with a triangular section and two calendered sheets are combined, but during the moulding operation the natural rubber substratum which is more plastic, penetrates by sliding between the covering pieces formed of copolymer and creates weak attack Zones just where the external stresses are high.

This inconvenience may be seen by operating as follows:

A 12.00-20 tire, after rasping, is retreaded with a cap obtained by straining following mix (1) Parts Ethylene-propylene copolymer Carbon black HAF 50 Cumyl peroxide 2.5 Sulfur 0.3

(1) Copolymer containing ethylene-propylene in the ratio of 1:1, with a molecular weight of about 100,000 and a Mooney plasticity (1+4 at 100 C.) of 50.

A side of the cap is spread with an adhesive obtained by dispersing in heptane the following mix (2) Parts Sulfochlorinated ethylene-propylene copolymer (sulfur content 1%, chlorine content 10%) 100 Natural rubber 20 Durosil (silicic acid) 50 TiO 20 MgO 2 DPG (diphenyl guanidine) 1.0 Sulfur 2.8 Tert. butyl cumyl peroxide 3.0

Amix (3) natural rubber having the following composition is then prepared:

This white mix (3) is drawn in the form of a sheet having a thickness of 0.8+1 mm. and is applied on the tread side on which the aforementioned chlorosulfonated copolymer adhesive (2) has previously been spread.

The tread provided with this substratum of white natural rubber (3) is wound upon the carcass spread with a commercial adhesive of the type normally used by retreaders.

The tread size is 230 x 16 mm. and only the central zone of the carcass is therefore retreaded.

Two strained pieces having a triangular section are then prepared from the copolymer mix (1) and provided with a substratum according to the aforementioned technique. They are then applied to the carcass to connect the central substratum with the tire sidewalls.

The tire is then kept at 170 C. for 2 hours. When the vulcanization is completed the tire is withdrawn from the mould and infiltration towards the outer side of the substratum are observed in the contact zones of the triangular strained pieces used for retreading.

The tire is successively used in the road abrasion tests. After a few kilometers of running a detaching is noted in correspondence with the aforementioned infiltrations.

Operating now with the following special technique, the above drawback is eliminated and good retreated tires are obtained.

For retreading a 12.00-20 tire a sheet of a black mix having the same composition as the tread or cap of mix 1 is inserted between same cap and the white substratum of natural rubber mix (3).

The substratum thus consisting of a sheet of white natural rubber (3) and a sheet of black copolymer (1) bonded together by a layer of chlorosulfonated adhesive mix (2), is directly applied to the carcass.

Successively the central tread strip and the two strained pieces having triangular section (for connecting the central tread strip with the tire side-walls) are applied in this order on the carcass.

When the vulcanization is completed, no white infiltration is noted. The tire, subjected to road tests, presents the characteristics of a tire retreaded with a tread which behaves as a single extruded piece.

The latter technique is particularly advantageous since, once the adhesion between the two substrates consisting of the black mix on the basis of copolymer and of a white mix on the basis of natural rubber is granted by the sulfochlorinated adhesive, it makes it possible to eliminate any other inconvenience and to carry out the retreading by applying more than one strained sheet onto the carcass.

In all the examples ethylene-propylene or ethylenebutene examples may be used interchangeably.

Many variations and modifications can of course be practiced without departing from the spirit of the present invention.

Having thus described the invention, what it is desired to secure and claim by Letters Patent is:

1. A process for vulcanizing and bonding an elastic saturated copolymer of ethylene and a higher alpha-olefin having the formula RCH CH=CH where R is selected from the group of hydrogen and methyl onto a layer of uncured natural rubber which comprises placing between the rubber to be cured and the saturated copolymer to be vulcanized and bonded to the rubber, an interlayer comprising a vulcanization adhesive consisting essentially of an elastomeric chlorosulfonated copolymer of ethylene and a higher alpha-olefin having the formula RCH CH=CH where R is selected from the group of hydrogen and methyl, an organic peroxide, a sulfur curing agent, uncured natural rubber and a reinforcing filler, subsequently heating the assembled members at a temperature ranging from 110 to 220 C. for a period of about ten to twenty minutes under pressure until said saturated copolymer layer and said rubber layer are covulcanized and a solid bond between the rubber layer and the saturated copolymer layer is obtained.

2. A process according to claim 1, in which the chloro sulphonated copolymer is dissolved in a hydrocarbon solvent prior to being placed between the uncured rubber layer and the saturated copolymer layer.

3. A process according to claim 1, in which said uncured natural rubber layer is a coating on a tire ply and in which said saturated copolymer layer is a tire tread.

4. A process according to claim 1, in which the saturated copolymer layer is a tire tread and in which prior to the vulcanization and bonding step said layer of uncured natural rubber is placed between the retread and a tire carcass.

5. A product comprising at least one layer of vulcanized copolymer of ethylene and higher alpha-olefin having the formula RCH-CH CI-b, where R is selected from the group of hydrogen and methyl, at least one layer of vulcanized natural rubber, said layers having been bonded together and covulcanized with an adhesive consisting essentially of a chlorosulfonated copolymer of ethylene and a higher alpha-olefin having the formula RCH -CH=CH where R is selected from the group consisting of hydrogen and methyl, an organ-ic peroxide, a sulfur curing agent, uncured natural rubber, and a reinforcing filler.

6. A product according to claim 5, in which the product is a tire and contains in addition to the layer of rubber and layer of copolymer, at least one tire ply and in which the said layer of copolymer is a tire tread and in which the layer of rubber is a coating on said tier ply and in which said tire ply is bonded to the tire tread by means of said adhesive and said coating of rubber.

7. A product according to claim 5, in which the product is a tire which contains a tire carcass, the copolymer layer is a retread, and in which the layer of rubber is a layer interposed between the retread and the tire carcass.

8. A product according to claim 5, in which the product is a conveyor belt containing at least one layer of cloth and the layer of rubber is a coating on said cloth.

References Cited by the Examiner UNITED STATES PATENTS 1,904,502 4/1933 Michelin 161-221 2,577,843 12/1951 Crosby et a1. 161-222 2,630,398 3/1953 Brooks et al 156-99 2,710,291 6/1955 Little 260-795 2,711,986 6/1955 Strain et al. 156-327 2,793,151 5/1957 Arnett 138-126 2,812,278 11/1957 Boger 156-333 2,822,026 2/ 1958 Willis 156-135 (Other references on following page) 1 1 UNITED STATES PATENTS Johnson et a1. 260--79.3 Berardinelli et a1. 117-12 Cole 156309 Grimminger et a1. 117--93.31 Merck et a1. 156-393 Snoddon et a1. 156-333 Rusignuolo et a1. 117138.8

FOREIGN PATENTS 10/1958 Canada.

1 2 OTHER REFERENCES Materials and Methods (Materials in Design Engineering), pp. 96100 cited, January 1957.

Report No. 564, September 1956, Hypalon 20, by 5 B. W. Fuller, pp. 21-23 cited.

ALEXANDER WYMAN, Primary Examiner. CARL F. KRAFFT, EARL M. BERGERT, Examiners.

10 R. J. ROCHE, Assistant Examiner. 

5. A PRODUCT COMPRISING AT LEAST ONE LAYER OF VULCANIZED COPOLYMER OF ETHYLENE AND HIGHER ALPHA-OLEFIN HAVING THE FORMULA RCH2-CH=CH2, WHERE R IS SELECTED FROM THE GROUP OF HYDROGEN AND METHYL, AT LEAST ONE LAYER OF VULCANIZED NATURAL RUBBER, SAID LAYERS HAVING BEEN BONDED TOGETHER AND COVULCANIZED WITH AN ADHESIVE CONSISTING ESSENTIALLY OF A CHLOROSULFONATED COPOLYMER OF ETHYLENE AND A HIGHER ALPHA-OLEFIN HAVING THE FORMULA RCH2-CH=CH2, WHERE R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND METHYL, AN ORGANIC PEROXIDE, A SULFUR CURING AGENT, UNCURED NATURAL RUBBER, AND A REINFORCING FILLER. 